Esters of 3-hydroxyindone compounds as herbicides and miticides

ABSTRACT

A new series of substituted esters of 3-hydroxyindone compounds have been found to have exceptional miticidal and herbicidal activity.

The novel compounds of this invention are 3-hydroxyindone compoundscorresponding to the following general formula: ##STR1## wherein: R¹ ishydrogen, halogen or an organic radical;

R² is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine,bromine, trichloromethyl or trifluoromethyl or mixed chlorofluoromethyl;

R³ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorine, bromine,nitro, acylamido, trichloromethyl or trifluoromethyl;

R⁴ is methyl, ethyl, methoxy, ethoxy, fluorine chlorine or bromine;

R⁵ is hydrogen, lower alkyl, lower haloalkyl, lower alkoxy, acylamido,fluorine, chlorine or bromine;

R⁶ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorine, bromine,trifluoromethyl, trichloromethyl, mixed chlorofluoromethyl or acylamido;

n is a small whole number from 1 to 4; and

R² and R⁵ or R³ and R⁵ may be taken together to form --CH═CH--CH═CH--,with the proviso that when R⁴ is ethyl, methoxy or ethoxy, R², R³ and R⁵may not all be hydrogen.

Compositions falling within the above generic formula exhibit biologicalactivity as pre-emergent herbicides to a greater or lesser extent. Someexhibit very powerful pre-emergent herbicidal activity in extremelysmall dosages while others require larger dosages to be effective.

Miticidal activity against both the adult mite and mite ova is limitedto a somewhat smaller class of compositions. In general, thecompositions exhibiting this type of biological activity are thosehaving the structural formula given above wherein:

R¹ is chlorine, bromine, fluorine or an organic radical, which does notinterfere with hydrolysis of the ester moiety to which it is attached;

R² is hydrogen, methyl, ethyl, methoxy, fluorine, chlorine or bromine;

R³ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorine orbromine;

R⁴ is methyl, ethyl, methoxy, fluorine, chlorine or bromine;

R⁵ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorine orbromine;

R⁶ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorine orbromine; and

n is a small whole number from 1 to 4, with the proviso that when R⁴ isethyl or methoxy, R², R³ and R⁵ may not all be hydrogen.

In general, these compositions also exhibit the highest degree ofherbicidal activity.

Activity is greatest in compounds having an alkyl or a halo substituentin an ortho position on the 2-phenyl moiety, especially when the alkylgroup is relatively small such as methyl or ethyl and preferably methyl.This is also true of alkoxy substituents and thus methoxy substituentsare preferred.

The most active miticidal compositions have at least one and preferablyboth ortho positions of the 2-phenyl moiety substituted with eitherlower alkyl or halogen. Compounds having no substituents in either orthoposition appear to be completely inactive both as miticides and asherbicides (See Table V). Compounds having only a single alkoxysubstituent and no other substituent on the 2-phenyl ring are inactiveor nearly so.

It has also been found that miticidal compositions of the classdescribed above, wherein R¹ is lower alkyl having no more than fourcarbon atoms have excellent fumigant properties, (See Table VII below),which are not shared by other members of the class.

In general, all of the new compositions are either totally lacking inphytotoxic effect or exhibit only minimal phytotoxic properties withrespect to economically important crop species tested. (See Table IX).

As indicated above, the R¹ substituent of the ester moiety may behalogen or essentially any organic radical including organic radicalshaving substituents such as halogen, nitro, alkyl, alkoxy, alkyl, thio,keto, cyano, amido etc. Illustrative of the wide range of permissible R¹functions are:

Alkyl, such as methyl, t-butyl, heptadecyl, pentadecyl, chloroethyl,cyanoethyl, nitropropyl, dibromopropyl and cyanopropyl

Alkenyl, such as vinyl, allyl and undecenyl

Alkynyl, such as ethynyl and propynyl

Cycloalkyl, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyland bicyclooctyl

Cycloalkenyl, such as cyclopentenyl, cyclohexenyl and methylcyclohexenyl

Alkylthioalkyl, such as methylthiomethyl, propylthioethyl,butylthioethyl and octylthiomethyl

Alkoxyalkyl, such as isopropoxymethyl, methoxymethyl and propoxyethyl

Alkoxycarbonylalkyl, such as methoxycarbonylpropyl,cyclohexyloxycarbonylethyl and butoxycarbonylbutyl

Arylalkyl such as benzyl, chlorobenzyl, nitrobenzyl, 3-phenylpropyl,phenylethyl, and 1-naphthylmethyl

Aryloxyalkyl such as phenoxyethyl, dichlorophenoxymethyl,methoxyphenoxyethyl and naphthyloxymethyl

Arylthioalkyl such as phenylthiomethyl and naphthylthiomethyl

Aryl such as phenyl, chlorophenyl, nitrophenyl, cyanophenyl,fluorophenyl, methoxyphenyl, trimethylphenyl and chloronaphthyl

Alkoxy such as methoxy, butoxy, chloromethoxy, octyloxy, dodecyloxy andethylhexyloxy

Alkylthio such as methylthio, isopropylthio and octylthio

Aryloxy such as phenoxy and chlorophenoxy

Arylthio such as phenylthio

Heterocyclic such as furyl, thenyl, morpholino, piperidino, pyridyl andpyrimidinyl

Amino such as dimethylamino, t-butylamino, methylphenylamino,2,4,6-trimethylphenylamino, cyclohexylmethylamino anddimethylallophanyl. By way of further illustration, the aminosubstituents can be radicals having the formula --NR⁷ R⁸, wherein R⁷ ishydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl and R⁸ is alkyl,alkenyl, alkynyl, cycloalkyl or aryl or R⁷ and R⁸, taken together, forma lower alkylene or lower dialkylene ether linkage.

Acylamidoalkyl such as acetamidomethyl and propionamidoethyl

Carbamoylalkyl such as carbamoylmethyl and N,N-dimethylcarbamoylethyl

From the test data below, it will be seen that within broad limits thecharacter of the R¹ group has little or no effect upon the activity ofthe enol ester composition. Steric effects of very large aliphaticsubstituents have a minimal influence on the activity of the respectiveacyloxyindone as compared to the cases where R¹ is lower alkyl (TableIV). However, when R¹ is phenyl having substituents in the two orthopositions, substantial impairment of both herbicidal and miticidalactivity results. This is clearly due to steric inhibition, however,this undesirable steric effect may be overcome by electronic effectssince compositions having substituents in both ortho positions and inthe meta position did have activity at relatively low doses. It isbelieved that the function of the ester grouping in the novelcompositions of this invention is to facilitate movement of thecomposition to the proper situs within the pest. The first step in theeventual destruction of the pest is believed to involve hydrolysis ofthe enol ester to the parent indanedione composition and, thus, thedegree to which the composition is susceptible to hydrolysis plays animportant role in its overall biological activity. Compositions whereinR¹ is a phenyl group substituted only in both ortho positions exhibitseverely reduced biological activity, presumably because they are notreadily hydrolyzable. The R¹ group is, therefore, preferably one inwhich the ester moiety is relatively hydrolyzable.

In general, enol ester compositions of this invention can be preparedconveniently by the reaction of an indandione with acid anhydride oracid halide in accordance with the following general reaction scheme:##STR2##

The reaction is preferably carried out in the presence of an acceptorsuch as N,N-dimethylaniline, pyridine, alpha-picoline, any lutidine,collodine or a tertiary aliphatic amine in a suitable solvent such asacetone, chloroform, toluene, dimethylformamide or the like. Inorganicbasis such as potassium carbonate may also be employed. The reaction isnot temperature sensitive and may be conducted over a broad range toyield the desired product.

The enol ester compositions in which R¹ is halogen can be prepared byreacting the appropriate indandione with the appropriate carbonylhalide. Enol ester compositions in which R¹ is amino are prepared byreacting the appropriate amine with a 3-halocarbonyloxy substitutedindone.

The indandiones used as starting materials in the preparation of theindone ester compounds of this invention can be prepared by reacting anappropriately substituted benzaldehyde composition with an appropriatelysubstituted phthalide composition as described in U.S. patentapplication Ser. No. 816,024 filed Apr. 14, 1969 and U.S. Pat. No.3,622,632.

The following representative specific examples are presented to moreclearly illustrate the methods used to prepare the novel compositions ofthis invention.

EXAMPLE I Preparation of 3-Acetoxy-2-(2',4',6'-Trimethylphenyl)Indone

A suspension of 2.64 g (0.01 mole) of2-(2',4',6'-trimethylphenyl)-1,3-indandione in 50 ml of acetic anhydridewas treated with two drops of pyridine. After stirring for three hoursthe solid had dissolved and the clear solution was concentrated in vacuoat 60°. The residue was taken up in ether, washed with cool potassiumbicarbonate solution and water, and the ether solution was dried overmagnesium sulfate. Filtration followed by evaporation produced a solidwhich was recrystallized from hexane to give the desired product, M.P.115°-116°.

EXAMPLE II Preparation of3-Isopropyloxycarbonyloxy-2-(2',4',6'-Trimethylphenyl)Indone

To a mixture of 9.2 g. (0.035 mole) of2-(2',4',6'-trimethylphenyl)-1,3-indandione, 4.0 g. of pyridine and 200ml. of hydrocarbon stabilized chloroform, was added dropwise withstirring, 4.3 g. (0.035 mole) of isopropyl chloroformate at 25°-30° C.After the addition was completed the reaction mixture was stirred atroom temperature for two days, then added to 200 ml. of 10 percenthydrochloric acid. The mixture was stirred for three minutes and thechloroform layer was separated and washed two times with water, thendried with magnesium sulfate. The chloroform was removed in vacuo andthe yellow oily residue was dissolved in n-hexane and treated withcharcoal for 10 minutes. This mixture was filtered and the filtrateconcentrated to a crystalline residue which was recrystallized fromisopropanol to give 10 g. of a yellow solid. M.P. 95°-96° C.

EXAMPLE III Preparation of2-(2',4',6'-Trimethylphenyl)-3-Pivaloyloxyindone

To a stirred slurry of 2128 g. (8.6 moles) of2-(2',4',6'-Trimethylphenyl)-1,3-indandione in 8000 ml of isopropylether was added 1420 g. (18 moles) of dry pyridine followed by 1089 g.(9 moles) of pivaloyl chloride. When addition of the pivaloyl chloridewas complete the reaction mixture was heated at reflux for 0.5 hour and,after cooling, the resulting solution was extracted with 2 × 2000 ml ofwater, 1 × 1000 ml of 50-volume percent hydrochloric acid, and againwith water. Concentration of the isopropyl ether solution in vacuoproduced, in three successive fractions, 2792 g. (93.2 percent) ofproduct, M.P. 105°-106°.

EXAMPLE IV Preparation of3-(2-Ethylhexanoyloxy)-2-(2',4',6'-Trimethylphenyl)Indone

A suspension solution of 520 grams (2.0 moles) of2-(2',4',6'-trimethylphenyl)-1,3-indandione in 2 liters of toluenecontaining 212 grams (2.1 moles) of triethylamine was stirred at roomtemperature for one hour and then 325 grams (2.0 moles) of2-ethylhexanoyl chloride was added with stirring at 30° to 40° (withsome cooling) over a period of 20 minutes. The resulting deep redmixture was stirred at 30° to 35° for three hours and then at roomtemperature overnight.

The by-product triethylamine hydrochloride was collected and washed withtoluene. The combined filtrates were washed with 10 percent hydrochloricacid and then with water until neutral. After drying over mangesiumsulfate, the toluene solution was concentrated to produce a solidresidue which was recrystallized from hexane with charcoal treatment.There was obtained 580 grams (75.2 percent) of product, M.P. 65°-67° C.

EXAMPLE V Preparation of3-Stearoyloxy-2-(2',4',6'-Trimethylphenyl)Indone

To a solution of 66 g. (0.25 mole) of2-(2',4',6'-trimethylphenyl)-1,3-indandione, 22 g. of pyridine and 600ml. of hydrocarbon stabilized chloroform was added dropwise withstirring at 25°-30° C., 76 g. (0.25 mole) of stearoyl chloride. Afterthe addition was completed, the reaction mixture was stirred for 20hours at 28° C. The mixture was then added to 500 ml. of 10 percenthydrochloric acid and stirred for 5 minutes. The chloroform layer wasseparated and washed two times with water then with 300 ml. of 5 percentpotassium bicarbonate and finally washed until neutral with water. Theorganic layer was dried with magnesium sulfate, and then the chloroformwas removed in vacuo. The yellow oily residue was dissolved in n-hexaneand allowed to stand at 28° C. for 3 hours while a small amount of solidseparated (starting 2-(2',4',6'-trimethylphenyl)-1,3-indandione). Thiswas removed and the filtrate concentrated to a very viscous oily residuewhich was treated with n-hexane and cooled to -10° C. The resultingcrystalline solid was filtered and washed with cold n-hexane to give 108g., M.P. 31°-32° C.

EXAMPLE VI Preparation of3-(2-Ethylhexyloxycarbonyloxy)-2-(2',4',6'-Trimethylphenyl)Indone

To a solution of 9.2 g. (0.035 mole) of2-(2',4',6'-trimethylphenyl)-1,3-indandione, 4.0 g. of pyridine, and 200ml. of hydrocarbon stabilized chloroform was added dropwise withstirring 6.8 g. (0.035 mole) of 2-ethylhexyl chloroformate at 25°-30° C.After the addition was completed, the reaction mixture was stirred at25°-30° C. for two days, then added to 200 ml. of 10 percenthydrochloric acid. The chloroform layer was separated and washed twotimes with water, then dried with magnesium sulfate. The chloroform wasstripped from the product under reduced pressure. The yellow oilyresidue was dissolved in 200 ml. of n-hexane and allowed to stand at 25°C. for three hours while a small amount of2-(2',4',6'-trimethylphenyl)-1,3-indandione separated. This solid wasremoved and the filtrate was treated with charcoal. The charcoal wasremoved by filtration and the filtrate was concentrated under reducedpressure (1.0 mm at 28°-30° C.). The product was a yellow oily residue(10 g.).

EXAMPLE VII Preparation of 3-(4-Chlorobutanoyloxy)-2-(2',4',6'-Trimethylphenyl)Indone

4-Chlorobutyrylchloride 4.9 g. (0.035 mole) was added dropwise withstirring at 25°-32° C. to a solution of 9.2 g. (0.035 mole) of2-(2',4',6'-trimethylphenyl)-1,3-indandione, 4.0 g. of pyridine and 200ml. of hydrocarbon stabilized chloroform. After the addition wascompleted, the mixture was stirred at 28° C. for 2 days, then added to200 ml. of 10 percent hydrochloric acid, and stirred for 2 minutes. Thechloroform layer was separated and washed two times with water, thendried with magnesium sulfate. The chloroform was removed from theproduct under reduced pressure. The resulting solid residue wasrecrystallized from isopropanol to give 11 g. of a yellow solid. M.P.98°-100° C.

EXAMPLE VIII Preparation of 3-Benzoyloxy-2-(2',6'-Dichlorophenyl)Indone

A stirred solution of 2-(2',6'-dichlorophenyl)-1,3-indandione (3.84 g.,0.0132 mole) in 13 ml. of pyridine was treated with benzoyl chloride(1.4 g., 0.01 mole) at room temperature. After the addition wascompleted the mixture was stirred at room temperature for 16 hours andthen poured into dilute hydrochloric acid. The precipitated solid wascollected by filtration and then dissolved in ether. The ether solutionwas washed with dilute hydrochloric acid and then with water (3 × 50ml.). The dried (MgSO₄) ether solution was evaporated under reducedpressure to furnish a solid residue which was recrystallized fromethanol to give 1.7 g. (33%) of3-benzoyloxy-2-(2',6'-dichlorophenyl)indone, M.P. 154°-156° C.

EXAMPLE IX Preparation of3-(2-Methylbenzoyloxy)-2-(2',4',6'-Trimethylphenyl)Indone

A mixture of 2-(2',4',6'-trimethylphenyl)-1,3-indandione (7.92 g. 0.03mole) and o-toluoyl chloride (5.1 g., 0.033 mole) in 30 ml. of pyridinewas stirred at room temperature for 20 hours. The mixture was pouredinto 300 ml. of 10% hydrochloric acid. The oil which separated wasextracted with ether and the ether extract was washed with water (2 × 75ml.). The dried MgSO₄) ether solution was evaporated under reducedpressure and the residue thus obtained was recrystallized from ethanolto afford 7.6 g. (66%) of product, M.P. 116°-118° C.

EXAMPLE X Preparation of3-(3-Nitrobenzoyloxy-2-(2',6'-Dichlorophenyl)Indone

A mixture of 2-(2',6'-dichlorophenyl)-1,3-indandione (8.73 g., 0.03mole) and m-nitrobenzoyl chloride (6.12 g., 0.033 mole) in 30 ml. ofpyridine was stirred at room temperature for 20 hours. The mixture wasadded to 300 ml. of 10% hydrochloric acid, and the precipitated solidwas collected by filtration. Recrystallization from ethanol afforded 8.0g. (61%) of the tile compound, m.p. 182°-185° C.

EXAMPLE XI Preparation of2-(2',4',6'-Trimethylphenyl)-3-Chlorocarbonyloxyindone

To a solution of 25 grams (0.25 mole) of phosgene in 200 ml of benzenewas added with stirring at 25° C a solution of 26 grams (0.1 mole) of2-(2',4',6'-trimethylphenyl)-1,3-indandione and 14 grams (0.11 mole) ofN,N-dimethylaniline in 200 ml of benzene over a 10 minute period. Theresulting mixture was stirred at 35° for 8 hours and then filtered. Theresulting filtrate was concentrated in vacuo and the yellow residual oilwas taken up in hexane and left overnight. After filtering, the hexanesolution was concentrated in vacuo to a residue which crystallized.After washing with cold hexane and drying this crystalline residueamounted to 25 grams (77 percent yield), M.P. 95°-97°. The infraredspectrum (Nujol) was consistent with the desired compound showing bondsat (μ): 5.6 (ClC(O)O--); 5.78 (keto C═O), 6.03 (C═C); 6.19 and 6.21(arom. C═C), 8.9 (C--O-- of ester); 11.25 (isolated arom. H); 13.1 (4adj. arom. H). The nmr spectrum (CDCl₃) showed the following bands (δ,ppm): 2.18, 2.22 (two singlets, ratio 2:1, 3 arom. CH₃, 9H); 6.92(singlet, isol. arom. H, 2H); 7.02-7.62 (complex mult., arom. H, 4H).

EXAMPLE XII Preparation of2-(2',4',6'-Trimethylphenyl)-3-n-(t-Butyl)Carbamoyloxyindone

To a solution of 12 grams (0.038 mole) of3-chlorocarbonyloxy)-2-(2',4',6'-trimethylphenyl) indone in 150 ml oftoluene was added dropwise with stirring at ambient temperature, 5.6grams (0.076 mole) of t-butylamine. After stirring for 1 hour at roomtemperature the reaction mixture was filtered and the filtrateconcentrated in vacuo to produce a yellow oily residue. This wasdissolved in ethyl ether, and, after a thorough water wash, the ethersolution was dried over magnesium sulfate, treated with charcoal andfinally filtered. This filtrate was concentrated in vacuo to give asolid residue which was recrystallized from isopropyl alcohol to provide8 grams (63.8 percent) of product, M.P. 145°-147°; ir., Nujol (μ): 2.98(NH); 5.61 (enol CO); 5.9 (keto CO), 6.02 (conj. C═C); 6.22 (arom. C═C);7.21, 7.23 (t--C(CH₃)₃); 8.9 (C--O--) nmr, CDCl₃ (δ, ppm): 1.19(singlet, C(CH₃)₃, 9H); 2.18, 2.24 (pair of singlets, ratio 2:1, arom.CH₃, 9H); 5.4 (broad singlet, NH, 1H); 6.89 (singlet, isol. arom. H.2H); 7.0-7.6 (complex mult., 4 arom. H, 4H).

EXAMPLE XIII Preparation of2-(2',4',6'-Trimethylphenyl)-3-(4-Morpholino)Carbonyloxyindone

Using the same procedure used in Example XII above, but substituting 6.6grams (0.076 mole) of morpholine for t-butylamine, there was obtained asa residual yellow solid, 11 grams (77 percent), M. P. 43°-47°. Theinfrared spectrum was consistent with proposed structure.

EXAMPLE XIV Preparation of2-(2',4',6'-Trimethylphenyl)-3-(2,4-Dimethylallophanoyloxy)Indone

To a mixture of 9.2 grams (0.035 mole) of2-(2',4',6'-trimethylphenyl)-1,3-indandione and 200 ml of toluene wasadded 4 grams (excess) of triethylamine and the resulting mixture wasstirred at ambient temperature for 30 minutes. To this stirred mixturewas then added 5.3 grams (0.035 mole) 2,4-dimethylallophanoyl chlorideand the resulting solution was heated at 45° for four hours after whichthe mixture was cooled and filtered. The filtrate was washed 4 timeswith water, dried over magnesium sulfate, and finally concentrated invacuo to a residue which was dissolved in hexane and treated withcharcoal. Removal of the hexane in vacuo produced a residual oil whichwas taken as product, 10 grams (75.5 percent yield); ir. (capillary)(μ): 2.95 (NH); 5.75 (enol carbamate C═O); 5.80 (ketone C═O); 5.83(shoulder --NHC(O)N); 6.09 (enol C═C); 6.25 (arom. C═C), 8.9/7.8C--O--).

EXAMPLE XV Preparation of Bis[2-(2',4',6'-Trimethylphenyl)Indon-3-yl]Carbonate

To a solution of 20 grams of phosgene in 200 ml of toluene was addeddropwise with stirring at ambient temperature a solution of 26 grams(0.1 mole) of 2-(2',4',6'-trimethylphenyl)-1,3-indandione and 12 grams(0.12 mole) of triethylamine in 200 ml of toluene. The mixture wasstirred at room temperature for 2 hours and was then concentrated toabout one-half volume. The remaining solution was washed twice with coldwater and then dried over magnesium sulfate. Filtration and subsequentconcentration of the filtrate in vacuo produced a yellow solid, 20 grams(72 percent yield), M.P. 221°-223°. The infrared and nmr spectra areconsistent with the proposed structure.

EXAMPLE XVI Preparation of 3-Acetoxy-2(2',6'-Dichlorophenyl)-4 (and 7-)-Methylindone

To a solution of 3.05 gram (0.01 mole) of2-(2',6'-dichlorophenyl)-4-methyl-1,3-indandione in 50 ml of aceticanhydride was added 3 drops of pyridine and the resulting yellowishsolution was stirred at room temperature for 3 hours. The mixture wasthen concentrated in vacuo to a solid residue which was taken up inether, and the resulting solution was washed with ice water and thendilute sodium bicarbonate solution and finally dried over magnesiumsulfate. Filtration and subsequent concentration of the filtrate invacuo to produce a yellow crystalline residue which was crystallizedfrom isopropyl ether to yield 2.3 grams (66.2 percent) of product, M.P.101°-120°. The infrared and nmr spectra were consistent with the desiredstructure. These, together with the elemental analysis, show thematerial to be a mixture of the isomers indicated in the title of thisExample.

The following specific compositions in addition to those described inthe Examples and in Tables I-IV below are illustrative of the newcompositions of this invention:

3-(3-cyanopropionyloxy)-2-(2',6'-dimethylphenyl)indone

3-(acetamidoacetyloxy)-2-(2'-chloro-4',6'-dimethyl)indone

3-(2-methyl-2-nitropropionyloxy)-2-(2',4',6'-trimethylphenyl)indone

3-(diphenylacetyloxy)-2-(2',6'-dichlorophenyl)indone

3-(4-cyanobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone

3-(4-methylthiobenzoyloxy)-2-(2'-methyl-6'-ethylphenyl)indone

3-acetoxy-2-(2',4'-dimethyl-6'-ethylphenyl)indone

3-(3-methylbutyryloxy)-2-(2'-chloro-6'-ethylphenyl)indone

3-crotonoyloxy-2-(2'-bromo-6'-chlorophenyl)indone

3-(2-butynoyloxy)-2-(2'-methoxy-6'-methylphenyl)indone

3-cyclobutanoyloxy-2-(2'-bromo-6'-methylphenyl)indone

1-cyclopent-2-enoyloxy-2-(2',6'-dibromophenyl)indone

3-(4-bromobutyryloxy)-2-(2',6'-dimethyl-4'-ethylphenyl)indone

3-(2-methylthiopropionyloxy)-2-(2',6'-dichloro-4-methylphenyl)indone

3-(3-ethoxybutyryloxy)-2-(2'-chloro-4',6'-diethylphenyl)indone

3-(3-ethoxycarbonylbutyryloxy)-2-(2'-bromo-6'-fluorophenyl)indone

3-(2-phenylbutyryloxy)-2-(2',6'-dibromo-4'-methylphenyl)indone

3-(3-phenoxypropionyloxy)-2-(2',6'-dichloro-4'-fluorophenyl)indone

3-phenylthioacetoxy-2-(2'-chloro-6'-methylphenyl)indone

3-benzoyloxy-2-(2',6'-dimethyl-4'-isopropylphenyl)indone

3-(4-bromobenzoyloxy)-2-(2',4'-dichloro-6'-methoxyphenyl)indone

3-(3-isopropylbenzoyloxy)-2-(2'-methyl-6'-trifluoromethylphenyl)indone

3-(4-ethoxybenzoyloxy)-2-[2'-(t-butyl)-6'-methylphenyl]indone

3-(3,5-dinitrobenzoyloxy)-2-(2',6'-dimethoxy-4'-methylphenyl)indone

3-formyloxy-2-(2'-ethyl-6'-methylphenyl)indone

3-chlorocarbonyloxy-2-(2',6'-dimethyl-4'-chlorophenyl)indone

3-(isobutyloxycarbonyloxy)-2-(2',4'-dimethyl-6'-chlorophenyl)indone

3-(ethylthiocarbonyloxy)-2-(2'-fluoro-6'-methylphenyl)indone

3-(phenoxycarbonyloxy)-2-(2'-ethoxy-4',6'-dimethylphenyl)indone

3-(phenylthiocarbonyloxy)-(2',6'-dimethyl-4'-trifluoromethylphenyl)indone

3-(N-isopropylcarbamoyloxy)-2-(2',6'-diethylphenyl)indone

3-(N-hexyl-N-ethylcarbamoyloxy)-2-(2'-bromo-6'-ethylphenyl)indone

3-(N-allyl-N-methylcarbamoyloxy)-2-(2',6'-dimethyl-4'-isopropylphenyl)indone

3-(N,N-dicrotylcarbamoyloxy)-2-(2'-methoxy-4',6'-dimethylphenyl)indone

3-(N,N-dipropargylcarbamoyloxy)-2-(2'-methyl-4',6'-diethylphenyl)indone

3-(N-cyclopentyl-N-methylcarbamoyloxy)-2-(2',6'-dimethyl-4'-chlorophenyl)indone

3-[N-(4-methylphenyl)-N-ethylcarbamoyloxy]-2-(2',6'-dimethyl-4'-methoxyphenyl)indone

3-(heptanoyloxy)-2-(2',4',6'-trimethyl-3'-ethylphenyl)indone

3-(2-ethylpentanoyloxy)-2-(2',4'-dimethyl-6'-chloro-3'-methoxyphenyl)indone

3-(3-hexenoyloxy)-2-(2',5'-dichloro-6'-methylphenyl)indone

3-(propynoyloxy)-2-(2',3',6'-trimethylphenyl)indone

3-(cyclopropanoyloxy)-2-(2',6'-dimethyl-3'-chlorophenyl)indone

3-(2-bicyclooct-5-encarbonyloxy)-2-(2',6'-dimethyl-3'-bromophenyl)indone

3-(6-chloroheptanoyloxy)-2-(2',6'-dimethyl-3'-methoxyphenyl)indone

3-(3-propylthiopropionyloxy)-2-(2',6'-dimethyl-3'-fluorophenyl)indone

3-(3-methoxypropionyloxy)-2-(2'-methyl-3'-chloro-6'-methoxyphenyl)indone

3-[3-(butoxycarbonyl)propionyloxy]-2-(2'-methyl-6'-trifluoromethyl-3'-fluorophenyl)indone

3-[(4-chlorophenyl)acetoxy]-2-(2',6'-dichloro-3'-bromophenyl)indone

3-[2-(2-chloro-4-methylphenoxy)propionyl]-2-(2'-ethyl-6'-methyl-3'-chlorophenyl)indone

3-(4-chlorophenylthioacetoxy)-2-(2',6'-dichloro-3',4'-dimethylphenyl)indone

3-(benzoyloxy)-2-(2',6'-dimethyl-3',4'-dichlorophenyl)indone

3-(2,4,5-trichlorobenzoyloxy)-2-(2',3',4',6'-tetramethylphenyl)indone

3-(3,5-dimethylbenzoyloxy)-2-(2',6'-dichloro-3'-methylphenyl)indone

3-(3,4,5-trimethoxybenzoyloxy)-2-(2',3',4'-trimethyl-6'-methoxyphenyl)indone

3-(4-nitro-3-methylbenzoyloxy)-2-(2',4',6'-trichloro-3'-methylphenyl)indone

3-(formyloxy)-2-(2',3'-diethyl-6'-methylphenyl)indone

3-(chlorocarbonyloxy)-2-(2',4',6'-trimethyl-3'-chlorophenyl)indone

3-(chloroethoxycarbonyloxy)-2-(2',4',6'-trimethylphenyl)indone

3-(ethoxycarbonylmethylthiocarbonyloxy)-2-(2'-chloro-6'-methylphenyl)indone

3-(allylthiocarbonyloxy)-2-(2',6'-dimethylphenyl)indone

3-(2,4-dichlorophenylthiocarbonyloxy)-2-(2',4'-dimethyl-6'-ethylphenyl)indone

3-[4-(acetamido)phenoxycarbonyloxy]-2-(2',6'-dimethyl-4'-ethyl-3'-chlorophenyl)indone

3-[N,N-di(n-propyl)carbamoyloxy]-2-(2',4',6'-trimethyl-3'-bromophenyl)indone

3-propionyloxy-2-(2',4',6'-trimethylphenyl)-5-ethyl indone

3-acetoxy-2-(2',6'-dichlorophenyl)-5-t-butylindone

3-(2-ethylhexanoyloxy)-2-(2',4',6'-trimethylphenyl)-4,6-dimethylindone

3-(cyclopropanecarbonyloxy)-2-(2',6'-dichlorophenyl)-5,6-dichloroindone

3-[2-ethoxycarbonyl-2-methylpropionyloxy]-2-(2',6'-dichlorophenyl)-4-chloro-5-methylindone

3-(pivaloyloxy)-2-(2',4',6'-trimethylphenyl)-5-bromoindone

3-(2-ethylhexanoyloxy)-2-(2',4',6'-trimethylphenyl)-5,7-dimethylindone

3-(pivaloyloxy)-2-(2',4',6'-trimethylphenyl)-5-fluoroindone

3-(isobutyroxy)-2-(2',6'-dimethylphenyl)-5-methoxyindone

3-(pivaloyloxy)-2-(2'-trichloromethyl-6'-methylphenyl)indone

3-(isobutyroxy)-2-(2'-trifluoromethyl-4',6'-dichlorophenyl)indone

3-acetoxy-2-(2',6'-dimethyl-4'-nitrophenyl)indone

3-(propionyloxy)-2-(2',6'-dichloro-4'-acetamidophenyl)indone

3-(butyryloxy)-2-(2'-methyl-4'-trifluoromethylphenyl)indone

3-(pivaloyloxy)-2-(2',6'-dichloro-4'-trichlorophenyl)indone

3-(pivaloyloxy)-2-(2',6'-dichloro-4'-chlorodifluoromethylphenyl)indone

3-acetoxy-2-(2'-dichlorofluoromethyl-4',6'-dichlorophenyl)indone

3-(benzoyloxy)-2-(2',4',6'-trimethyl-3'-formamidophenyl)indone

3-acetoxy-2-(2',4'-dimethyl-5'-trifluoromethylphenyl)indone

3-(butyryloxy-2-(2',4',6'-trichloro-3'-dichlorofluoromethylphenyl)indone

3-(4-chloronaphthylcarbonyloxy)-2-(2',4',6'-trimethylphenyl)indone

3-(methoxycarbonyloxy)-2-(2'-methylphenyl)indone

3-(propoxycarbonyloxy)-2-(2',6'-diethylphenyl)indone

3-(isopropylthiocarbonyloxy)-2-(2'-chloro-6'-ethylphenyl)indone

3-(methoxyethylthiocarbonyloxy)-2-(2',4',6'-trimethylphenyl)indone3-(2,4-dimethylphenoxycarbonyloxy)-2-(2',6'-dimethylphenyl)indone

3-(pyrimidin-5-yl carbonyloxy)-2-(2'-bromophenyl)indone

3-(3-propionamidoethylcarbonyloxy)-2-(2',6'-dichlorophenyl)indone

3-(carbamoylmethylcarbonyloxy)-2-(2',4',6'-trimethylphenyl)indone

3-(N,N-dimethylcarbamoylethylcarbonyloxy)-2-(2'-chloro-6'-bromophenyl)indone

3-(2-nitroethylcarbonyloxy)-2-(2'-ethyl-6'-methylphenyl)indone

3-(3-cyanobutyryloxy)-2-(2'-bromo-6'-fluorophenyl)indone

3-(2,3-dibromopropionyloxy)-2-(2',4',6'-trimethylphenyl)indone

3-(acryloyloxy)-2-(2',6'-dimethylphenyl)indone

3-(propioloyloxy)-2-(2'-bromo-6'-methylphenyl)indone

3-(2-norborn-5-enecarbonyloxy)-2-(2',6'-dichlorophenyl)indone

3-(cycloheptanecarbonyloxy)-2-(2'-bromo-6'-methylphenyl)indone

3-(octylthioacetoxy)-2-(2',6'-dibromophenyl)indone

3-(3-isopropoxypropionyloxy)-2-(2',4',6'-triethylphenyl)indone

3-(3-cyclohexyloxycarbonylpropionyloxy)-2-(2'-bromo-6'-ethylphenyl)indone

3-(3-nitrophenylacetyloxy)-2-(2',6'-dimethylphenyl)indone

3-(1-naphthaleneacetyloxy)-2-(2',4',6'-trimethylphenyl)indone

3-(2-naphthyloxyacetoxy)-2-(2'-bromophenyl)indone

3-[3-(1-naphthylthio)propionyloxy]-2-(2',4',6'-trimethylphenyl)indone

Selected enol ester compounds, representative of those useful inaccordance with this invention were tested with respect to theirmiticidal and herbicidal activity.

Suspensions of the test compounds were prepared by dissolving one gramof compound in 50 milliliters of acetone in which had been dissolved 0.1gram (10 percent of the weight of compound) of an alkylphenoxyethanolsurfactant, as an emulsifying or dispersing agent. The resultingsolution was mixed into 160 milliliters of water to give roughly 200milliliters of a suspension containing the compound in finely dividedform. The thus-prepared stock suspension contained 0.5 percent by weightof compound. The test concentrations employed in the tests describedhereinbelow were obtained by diluting the stock suspension with water.The test procedures were as follows:

Mite Foliage Spray Test

Adults and nymphal stages of the two-spotted mite (tetranychus urticae(Koch)), reared on Tendergreen bean plants at 80°±5° F. and 50±5 percentrelative humidity, were the test organisms. Infested leaves from a stockculture were placed on the primary leaves of two bean plants 6 to 8inches in height, growing in a 21/2 inch clay pot. 150-200 Mites, asufficient number for testing, transferred from the excised leaves tothe fresh plants in a period of twenty-four hours. Following the 24 hourtransfer period, the excised leaves were removed from the infestedplants. The test compounds were formulated by diluting the stocksuspension with water to provide suspensions containing the desiredamount of test compound per million parts of final formulation. Thepotted plants (one pot per compound) were placed on a revolvingturntable and sprayed with 100-110 milliliters of test compoundformulation by use of a DeVilbis spray gun set at 40 psi. air pressure.This application, which lasted 30 seconds, was sufficient to wet theplants to run-off. As a control, 100-110 milliliters of a water solutioncontaining acetone and emulsifier in the same concentrations as the testcompound formulation, but containing no test compound, were also sprayedon infested plants. The sprayed plants were held at 80°±5° F. and 50±5percent relative humidity for 4 days, after which, a mortality count ofmotile forms was made. Microscopic examination for motile forms was madeon the leaves of the test plants. Any individual which was capable oflocomotion upon prodding was considered living.

Mite Ovicide Test

The test organism was the egg of the two-spotted mite (Tetranychusurticae (Koch)), as obtained from adults reared on Tendergreen beanplants under controlled conditions of 80°±5° F. and 50±5 percentrelative humidity. Heavily infested leaves from a stock culture wereplaced on the primary leaves of two bean plants 6 to 8 inches in height,growing in a two-and-a-half inch clay pot. Females were allowed tooviposit for a period of 48 hours and then the leaves of the infestedplants were dipped in a solution containing 800 parts of tetraethylpyrophosphate per million parts of water in order to destroy thereproductory forms and thus prevent further egg laying. This solution oftetraethyl pyrophosphate does not affect the viability of the eggs. Theplants were allowed to dry thoroughly. The test compounds wereformulated by diluting the stock suspension with water to give asuspension containing varying amounts of test compound per million partsof final formulation. The potted plants (one pot per compound) wereplaced on a revolving turntable and sprayed with 100-110 milliliters oftest compound formulation by use of a DeVilbis spray gun set at 40 psig.air pressure. This application, which lasted 30 seconds, was sufficientto wet the plants to run-off. As a control, 100-110 milliliters of awater solution containing acetone and emulsifier in the sameconcentrations as the test compound formulation, but containing no testcompound, were also sprayed on plants infested with eggs. The sprayedplants were held at 80°±5° F. and 50±5 percent relative humidity for 4days, after which a microscopic examination was made of unhatched (dead)and hatched (living) eggs.

Compositions were rated on the basis of percent kill with a rating of 1indicating no injury; 3 signifying an approximately 50% mortality and 5indicating 100% mortality at the indicated dosage.

Preliminary Herbicide Seed Germination Test

The following seeds were used in this test:

Perennial rye grass -- Solium perenne

Crabgrass -- Digitaria sanguinalis

Red root pigweed -- Amaranthus retroflexus

Mustard -- Brassica pincea var. foliosa (Florida broadleaf)

Two seed-soil mixtures were prepared as follows:

Mixture I

196 cc. Rye grass seed

75 cc. Mustard seed

18,000 cc. Sifted, fairly dry soil

Mixture II

99 cc. Crabgrass seed

33 cc. Amaranthus

18,000 cc. Sifted, fairly dry soil

Each of above mixtures is rolled separately in 5 gallon containers forapproximately one-half hour on ball mill to insure uniform mixing ofseeds and soil. For each compound four 3-inch pots are filled with soilto within 11/2 inches of top of pots. To 2 of these pots are added 70cc. of Mixture I. To the remaining 2 pots are added 70 cc. of MixtureII. The seed-soil mixture is tamped firmly, and the pots are removed tothe greenhouse and watered lightly. About 2 hours after planting, 25milliliters of the test formulation were added to each of 2 pots foreach soil-seed mixture; i.e., one replicate of each seed mixture perconcentration. An equal volume of a water solution containing acetoneand an emulsifier in the same concentration as the herbicidal mixturebut without the candidate herbicide is also added to each of thesoil-seed mixtures. These pots are used as check or control units. Thetest compounds are formulated by standard procedure of solution inacetone, addition of an emulsifier, and dilution with water. Tests wereconducted on all compositions at low concentration (100 ppm.). Certaincompositions were also tested at high concentration (1000 ppm). The potswere held in the greenhouse and watered lightly until results weretaken. Ten to 12 days after application of chemical, injury is noted foreach species by comparing treated vs. untreated pots. Ratings are madeat both the high and the low concentrations (1000 ppm and 100 ppm)according to the following designations:

5 = no seedlings emerged

4 = few seedlings emerged and/or very severe stunting

3 = moderate reduction in stand and/or moderate stunting

2 = very slight reduction in stand and/or slight stunting

1 = no injury; seedlings appear no different with respect to stand orgrowth than untreated controls

Accordingly, the maximum rating for one test seed species tested at bothhigh and low concentration is 10 and the maximum possible totalpreemergence rating is 40 (10 for each of the four test seed species).For those tested only at low concentration, the maximum rating is 20. Inthe Tables below, herbicidal test results are shown as a fraction inwhich the numerator is the actual rating achieved. In some tests thecrabgrass experiment was omitted. In these tests the maximum totalrating for species tested at both high and low concentrations is 30 and15 for species tested only at low concentrations.

In Table I below all of the compounds tested have a methyl substituentin each of the 2,4 and 6 positions on the 2-phenyl moiety and asubstituted phenyl group directly bonded to the carbonyl of the estergroup. This Table illustrates the effect of varying the number andposition of substituents on an aryl group attached to the ester moiety.

Table II is similar to Table I but differs in that the 2-phenyl moietycarries a chloro substituent at each of the 2 and 6 positions.

In Table III all of the compounds tested include an alkyl group attachedto the carbonyl of the ester while the 2-phenyl moiety is variouslysubstituted, but always includes a substituent in one of the orthopositions of the 2 phenyl moiety.

In Table IV below the 2-phenyl moiety of all of the compounds testedcarries methyl substituents at the 2, 4 and 6 positions and differ fromeach other only in the character of the ester moiety. The examplesillustrate the nature and extent of the influence of the ester functionon the biological properties of the enol ester compounds. It is to benoted that even those few compounds exhibiting little or no activity inthese particular tests will be somewhat effective at higher dosagelevels.

                                      TABLE I                                     __________________________________________________________________________     ##STR3##                                                                                                                            Primary                                                         ° C    Mite Data              Name                             R       M.P.   Herbicide                                                                            Adult                                                                             Ova                __________________________________________________________________________    3-Benzoxyloxy-2-(2',4',6'-trimethylphenyl)indone                                                               H       147-150                                                                              31/40  5   5                  3-(2-Chlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                      2-Cl    108-110                                                                              32/40  5   5                  3-(3-Chlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                      3-Cl    140-142                                                                              29/40  5   5                  3-(4-Chlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                      4-Cl    93-95  24/30  5   5                  3-(2-Methylbenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                      2-CH.sub.3                                                                            116-118                                                                              19/30  5   5                  3-(3-Methylbenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                      3-CH.sub.3                                                                            115-117                                                                              26/40  5   5                  3-(4-Methylbenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                      4-CH.sub.3                                                                            113-116                                                                              22/30  5   5                  3-(3-Methoxybenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                     3-OCH.sub.3                                                                           112-115                                                                              25/30  5   5                  3-(4-Methoxybenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                     4-OCH.sub.3                                                                           117-120                                                                              21/30  3   5                  3-(3-Nitrobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                       3-NO.sub.2                                                                            123-126                                                                              28/30  5   5                  3-(4-Nitrobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone                                                       4-NO.sub.2                                                                            165-167                                                                              26/30  5   5                  3-(2,4-Dichlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                       2,4-Cl.sub.2                                                                          126-128                                                                              32/40  5   5                  indone                                                                        3-(3,4-Dichlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                       3,4-Cl.sub.2                                                                          157-159                                                                              32/40  5   5                  indone                                                                        3-(3,5-Dichlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                       3,5-Cl.sub.2                                                                          165-168                                                                              23/30  5   5                  indone                                                                        3-(2,6-Dichlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                       2,6-Cl.sub.2                                                                          168-172                                                                               8/40  1   1                  indone                                                                        3-(2,3,6-Trichlorobenzoyloxy)-2-(2' ,4',6'-trimethylphenyl)-                                                   2,3,6-Cl.sub.3                                                                        163-165                                                                              21/40  1   3                  indone                                                                        3-(2,6-Dimethoxybenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                      2,6-(CH.sub.3 O).sub.2                                                                141-143                                                                               4/20  1   1                  indone                                                                        3-(2,4-Dimethylbenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                       2,4-(CH.sub.3).sub.2                                                                  118-120                                                                              11/15  1   5                  indone                                                                        3-(2,4,6-Trimethylbenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                    2,4,6-(CH.sub.3).sub.3                                                                154-155                                                                              10/15  1   1                  indone                                                                        3-(2,6-Dimethylbenzoyloxy)-2-(2',4',6'-trimethylphenyl)-                                                       2,6-(CH.sub.3).sub.2                                                                  123-125                                                                               4/20  1   1                  indone                                                                        __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR4##                                                                                                                            Mite                   Name                             R       M.P.   Herbicide                                                                            Adult                                                                             Ova                __________________________________________________________________________    3-(Benzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                                  H       154-156                                                                              32/40  5   5                  3-(2-Chlorobenzyloyloxy)-2-(2',6'-dichlorophenyl)indone                                                        2-Cl    106-108                                                                              30/40  5   5                  3-(3-Chlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                          3-Cl    124-126                                                                              32/40  5   5                  3-(4-Chlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                          4-Cl    113-116                                                                              23/30  5   5                  3-(2-Methylbenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                          2-CH.sub.3                                                                            Residue*                                                                             31/40  5   5                                                           Product                              3-(3-Methylbenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                          3-CH.sub.3                                                                            138-141                                                                              29/40  5   5                  3-(4-Methylbenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                          4-CH.sub.3                                                                            136-140                                                                              22/30  5   5                  3-(3-Methoxybenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                         3-OCH.sub.3                                                                           143-145                                                                              23/30  5   5                  3-(4-Methoxybenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                         4-OCH.sub.3                                                                           149-152                                                                              22/30  5   5                  3-(3-Nitrobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                           3-NO.sub.2                                                                            182-195                                                                              26/30  5   5                  3-(4-Nitrobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                           4-NO.sub.2                                                                            164-167                                                                              25/30  5   5                  3-(2,4-Dichlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                      2,4-Cl.sub.2                                                                          138-140                                                                              28/40  5   5                  3-(3,4-Dichlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                      3,4-Cl.sub.2                                                                          130-132                                                                              29/40  5   5                  3-(3,5-Dichlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                      3,5-Cl.sub.2                                                                          125-130                                                                              24/30  5   5                  3-(2,6-Dichlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone                                                      2,6-Cl.sub.2                                                                          182-185                                                                               8/40  1   1                  3-(2,3,6-Trichlorobenzoyloxy)-2-(2',6'-dichloro-                                                               2,3,6-Cl.sub.3                                                                        210-214                                                                              20/40  5   5                  phenyl)indone                                                                 3-(2,6-Dimethoxybenzoyloxy)-2-(2',6'-dichloro-                                                                 2,6-(CH.sub.3 O).sub.2                                                                226-228                                                                              12/15  1   1                  phenyl)indone                                                                 3-(2,4-Dimethylbenzoyloxy)-2-(2',6'-dichloro-                                                                  2,4-(CH.sub.3).sub.2                                                                  152-154                                                                               5/20  1   3                  phenyl)indone                                                                 3-(2,4,6-Trimethylbenzoyloxy)-2-(2',6'-dichloro-                                                               2,4,6-(CH.sub.3).sub.3                                                                142-145                                                                               6/15  1   1                  phenyl)indone                                                                 3-(2,6-Dimethylbenzoyloxy)-2-(2',6'-dichloro-                                                                  2,6-(CH.sub.3).sub.2                                                                  150-152                                                                               4/20  1     1**              phenyl)indone                                                                 __________________________________________________________________________     *Calcd for C.sub.22 H.sub.9 Cl.sub.5 O.sub.3 ; C, 67.65; H, 3.45; Found C     67.03; H, 3.72 γmax: 5.7μ (ester CO); 6.1μ (enol double bond)     5.82μ (ketone CO); 8.2μ (CO stretch).                                   **About 20% kill at 500 ppm.                                             

                                      TABLE III                                   __________________________________________________________________________                                              Mite                                Name                      M.P. ° C or IR                                                                   Herbicides                                                                          Adult                                                                             Ova                             __________________________________________________________________________    2-(2',6'-Dichlorophenyl)-3-(pivaloyloxy)indone                                                           133-135  30/40 5   5                               2-(2'-Bromophenyl)-3-(pivaloyloxy)indone                                                                 91-98    14/40 5   5                               3-Acetoxy-2-(2'-bromophenyl)indone                                                                       93-97    19/40 5   5                               3-(2-Ethylhexanoyloxy)-2-(2'-fluorophenyl)indone                                                         γmax (μ):                                                                      4/20 3   5                                                         5.61 (ester C═O);                                                         5.8 (ketone C═O);                                                         6.1 (enol C═C)                                  2-(2'-Chlorophenyl)-3-(pivaloyloxy)indone                                                                80-82    18/40 5   5                               2-(2'-Chlorophenyl)-3-(2-methylpentanoyloxy)indone                                                       γmax (μ):                                                                      4/20 5   5                                                         5.62 (ester C═O),                                                         5.8 (ketone C═O);                                                         6.1 (enol C═C)                                  2-(2'-Chlorophenyl)-3-(stearoyloxy)indone                                                                50-53     4/20 1   5                               2-(2'-Chloro-6'-methylphenyl)-3-(pivaloyloxy)indone                                                      93-96    33/40 5   5                               2-(2'-Methylphenyl)-3-(pivaloyloxy)indone                                                                 62      20/40 5   5                               3-(2-Ethylhexanoyloxy)-2-(2'-methylphenyl)indone                                                         γmax (μ ):                                                                     4/20 3   5                                                         5.65 (enol ester);                                                            5.81 (ketone C═O);                                                        6.11 (enol C═C)                                 2-(2'-Methylphenyl)-3-(palmitoyloxy)indone                                                               34-36     4/20 3   5                               2-(2'-Methylphenyl)-3-(neodecanoyloxy)indone                                                             γmax (μ):                                                                      4/20 1   1                               (mixture of isomers)      5.62 (ester C═O);                                                         5.79 (ketone C═O);                                                        6.1       (enol C═C)                            2-(2',4'-Dimethylphenyl)-3-(stearoyloxy)indone                                                           γmax (μ):                                                                     14/20 3   5                                                         5.6 (ester C═O);                                                          5.79 (ketone C═O);                                                        6.1 (enol C═C)                                  2-(2',4'-Dimethylphenyl)-3-(lauroyloxy)indone                                                            γmax (μ):                                                                     14/20 5   5                                                         5.6 (ester C═O);                                                          5.79 (ketone C═O),                                                        6.1 (enol C═C)                                  2-(2',4'-Dimethylphenyl)-3-(2-methylpentanoyloxy)-                                                       γmax (μ):                                                                     14/20 3   5                               indone                    5.62 (ester C═O);                                                         5.79 (ketone C═O);                                                        6.13 (enol C═C)                                 2-(2',6'-Dimethylphenyl)-3-(pivaloyloxy)indone                                                           82-84    31/40 5   5                               2-(2',5'-Dimethylphenyl)-3-(neodecanoyloxy)indone                                                        γmax (μ):                                                                      4/20 1   3                               (mixture of isomers)      5.63 (ester C═O);                                                         5.8 (ketone (C═O);                                                        6.1 (enol C'C)                                      2-2',5'-Dimethylphenyl)-3-(2-ethylbutanoyloxy)-                                                          γmax (μ):                                                                      4/20 3   5                               indone                    5.65 (ester C═O);                                                         5.8 (deonte C═O);                                                                   6.1 (enol C═C)                        2-(2',5'-Dimethylphenyl)-3-(tridecanoyloxy)indone                                                        γmax (μ):                                                                      4/20 1   5                                                         5.6 (ester C═O);                                                          5.8 (ketone C═O);                                                         6.1 (enol C═C)                                  2-(2'-Ethyl-6'-methylphenyl)-3-(pivaloyloxy)indone                                                       69-70    14/15 5   5                               2-(2',6'-Diethylphenyl)-3-(pivaloyloxy)indone                                                            98-99    12/15 5   5                               2-(2',6'-Dimethyl-4'-t-butylphenyl)-3-(pivaloyloxy)-                                                     129-133   9/40 1   1                               indone                                                                        2-(2',6'-Dimethyl-4'-methoxyphenyl)-3-(pivaloyloxy)-                                                     123-124  24/40 3   3                               indone                                                                        3-(Pivaloyloxy)-2-(6'-methoxy-2',3',4'-trimethylphenyl)-                                                 108-110  16/40 1   1                               indone                                                                        3-(2-Ethylhexanoyloxy)-2-(1-Naphthyl)indone                                                              γmax (μ):                                                                     14/20 1   1                                                         5.67 (ester C═O);                                                         5.81 (ketone C═O);                                                        6.15 (enol C═C)                                 3-(Acetoxy)-4(7)-methyl-2-(2',6'-dichlorophenyl)-                                                        101-120  37/40 5   5                               indone                                                                        2-(2',6'-Dichlorophenyl-4(7)-methyl-3-(pivaloyloxy)-                                                     152-154  20/40 1   3                               indone                                                                        2-(2',6'-Dichlorophenyl)-5(6)-methyl-3-(pivaloyloxy)-                                                    158-160  24/40 5   5                               indone                                                                        __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________     ##STR5##                                                                                                                      Mite                         Name                   M. P. ° C or IR                                                                            Herbicide                                                                           Adult                                                                             Ova                      __________________________________________________________________________    2-(2',4',6'-Trimethylphenyl)-3-                                                                      115-116             39/40 5   5                        (acetoxy)indone                                                               2-(2',4',6'-Trimethylphenyl)-3-                                                                      109-110.5           32/40 5   5                        (propionyloxy)indone                                                          2-(2',4',6'-Trimethylphenyl)-3-                                               (isobutyloxy)indone    78-80               37/40 5   5                        2-(2',4',6'-Trimethylphenyl)-3-                                               (pivaloyloxy)indone    100-102             32/40 5   5                        2-(2',4',6'-Trimethylphenyl)-3-                                               (2-ethylhexanoyloxy)indone                                                                           66-68               29/40 5   5                        2-(2',4',6'-Trimethylphenyl)-3-                                                                      62-65               31/40 5   5                        (cyclohexanoyloxy)indone                                                      2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.62 (ester CO);                                                               10/20 5   5                        (neodecanoyloxy)indone 5.78 (ketone CO); 6.1                                  (mixture of isomers)   (enol CC)                                              2-(2',4',6'-Trimethylphenyl)-3-                                               (Isopropoxycarbonyloxy)indone                                                                        95-96               18/20 5   5                        2-(2',4',6'-Trimethylphenyl)-3-                                               (octadecanoyloxy)indone                                                                              34                  19/20 5   5                        2-(2',4',6'-Trimethylphenyl)-3-                                                                      98-100              19/20 5   5                        (methylthioacetoxy)indone                                                     2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.60 (enol ester                                                               15/15 5   5                        (3-methoxycarbonylpropionyloxy)indone                                                                5.78 (ketone and ester (CO);                                                  6.08 (enol CC)                                         2-(2',4',6'-Trimethylphenyl)-3-                                                                      98-100              14/15 5   5                        (4-chlorobutyryloxy)indone                                                    2-(2',4',6'-Trimethylphenyl)-3-                                                                      115-117             15/15 5   5                        (methoxyacetoxy)indone                                                        2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.62 (enol ester                                                               11/15 5   5                        (endo-exo norborn-5-en-2-                                                                            5.79 (ketone CO); 6.09 (enol                           carbonyloxy)indone     CC)                                                    2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.59 (enol ester                                                               19/20 5   5                        (phenylacetoxy)indone  5.79 (ketone CO); 6.09 (enol                                                  CC)                                                    2-(2',4',6'-Trimethylphenyl)-3-                                                                      117-119             14/20 3   5                        (dimethylcarbamoyloxy)indone                                                  2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ); 5.59 (enol ester                                                               17/20 5   5                        (dodecanoyloxy)indone  5.79 (ketone CO); 6.09 (enol                                                  CC)                                                    2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.61 (enol ester                                                               19/20 5   5                        (undec-9-enoyloxy)indone                                                                             5.81 (ketone CO); 6.09 (enol                                                  CC)                                                    2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.60 (enol ester                                                               16/20 5   5                        (octyloxycarbonyloxy)indone                                                                          5.79 (ketone CO); 6.09 (enol                                                  CC)                                                    2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.61 (enol ester                                                               17/20 5   5                        (dodecyloxycarbonyloxy)indone                                                                        5.80 (ketone CO); 6.10 (enol                                                  CC)                                                    2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ ): 5.61 (enol ester                                                              15/20 5   5                        (2-ethylhexyloxycarbonyloxy)indone                                                                   CO); 5.79 (ketone CO);                                                        6.09 (enol CC)                                         2-(2',4',6'-Trimethylphenyl)-3-                                                                      43-45               13/15 5   5                        (octadecyloxycarbonyloxy)indone                                               2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.65 Sh (enol                                                                  11/15 5   5                        (octylthiocarbonyloxy)indone                                                                         CO); 5.78 (ketone CO);                                                        6.08 (enol CC)                                         2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.60 (enol ester                                                               11/15 5   5                        (cyclopent-2-en-1-ylacetoxy)indone                                                                   CO); 5.80 (ketone (CO);                                                       6.08 (enol CC)                                         2-(2',4',6'-Trimethylphenyl)-3-                                                                      78-80               15/15 5   5                        (butyryloxy)indone                                                            2-(2',4',6'-Trimethylphenyl)-3-                                                                      67-79               15/15 5   5                        (pentanoyloxy)indone                                                          2-(2',4',6'-Trimethylphenyl)-3-                                                                      153-155             17/20 5   5                        (2-furoyloxy)indone                                                           2-(2',4',6'-Trimethylphenyl)-3-                                                                      151-153             18/20 5   5                        (2-thenoyloxy)indone                                                          2-(2',4',6α-Trimethylphenyl)-3-                                                                110-112             18/20 5   5                        (3-pyridinecarbonyloxy)-                                                      indone                                                                        2-(2',4',6'-Trimethylphenyl)-3-                                                                      95-97               13/20 5   5                        (chlorocarbonyloxy)indone                                                     2-(2',4',6'-Trimethylphenyl)-3-                                                                      97-98               19/20 5   5                        (4-chlorophenyloxycarbonyloxy)indone                                          2-(2',4',6'-Trimethylphenyl)-3-                                                                      145-157             15/20 5   5                        (N-(t-butyl)carbamoyloxy)indone                                               2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.82 (enol ester                                                                4/20 1   1                        (N-butyl-N-methylcarbamoyloxy)indone                                                                 CO); 5.88 (ketone CO);                                                        6.07 (enol CC)                                         2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.84 (enol ester                                                               10/20 3   1                        (N,N-di(butyl)carbamoyloxy)indone                                                                    CO); 5.88 (ketone CO);                                                        6.19 (enol (CC)                                        2-(2',4',6'-Trimethylphenyl)-3-                                                                      120-122             10/20 1   3                        (N-methyl-N-phenylcarbamoyloxy)indone                                         2-(2',4',6'-Trimethylphenyl)-3-                                                                      43-47                4/20 3   5                        (4-(morpholino)carbonyloxy)indone                                             2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.76 (enol ester                                                                4/20 1   3                        (piperdinocarbonyloxy)indone                                                                         CO); 5.82 (ketone CO;                                                         6.10 (enol CC)                                         2-(2',4',6'-Trimethylphenyl)-3-                                                                      152-155              4/20 5   5                        (N-(2,4,6-Trimethylphenyl)-                                                   carbamoyloxy)indone                                                           2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.62 (enol ester                                                               16/20 5   5                        (N-cyclohexyl-N-methylcarbamoyloxy)-                                                                 CO); 5.85 (ketone CO);                                 indone                 6.12 (enol CC)                                         2(2',4',6'-Trimethylphenyl)-3-                                                                       113-115             20/20 5   5                        (2,4-dichlorophenoxyacetoxy)indone                                            2-(2',4',6'-Trimethylphenyl)-3-                                                                      221-223             15/20 5   5                        (3-(2-(2,4,6-trimethylphenyl)-                                                indon)yloxycarbonyloxy)indone                                                 2-(2',4',6'-Trimethylphenyl)-3-                                                                      γmax (μ): 5.71 (enol ester                                                               16/20 1   5                        (2,4-dimethylallophanoyloxy)indone                                                                   CO); 5.8 (ketone CO);                                                         6.09 (enol CC)                                         __________________________________________________________________________

The data presented in Table V below demonstrates the importance ofsubstitution in the ortho position of the 2-phenyl moiety to achievebiological activity. None of the enol ester compounds described in TableV are substituted in the ortho position. A few are substituted in thepara position. All were completely devoid of miticidal or herbicidalactivity.

The data presented in Table VI below illustrates the importance of thenature of substituents in the ortho position on the 2-phenyl moiety. Allof the enol ester compounds described in Table VI are eithermonosubstituted in only the ortho position with alkoxy, trifluoromethylor alkyl (having more than one carbon atom) or are disubstituted only inthe ortho positions with alkyl groups (having more than two carbonatoms). None of these compounds exhibits any miticidal or herbicidalactivity.

                                      TABLE V                                     __________________________________________________________________________                                               Mite                               Name                  M. P. ° C or IR                                                                       Herbicide                                                                           Adult                                                                             Ova                            __________________________________________________________________________    3-(2-Ethylhexanoyloxy)-2-phenyl-                                                                    γmax (μ): 5.61 (ester C═O);                                                     4/20  1   1                              indone                5.8 (ketone C═O); 6.12                                                    (enol C═C)                                          2-Phenyl-3-(stearoyloxy)indone                                                                      63-64          4/20  1   1                              2-Phenyl-3-(pivaloyloxy)indone                                                                      102-104        8/40  1   1                              2-Phenyl-3-(acetoxy)indone                                                                          114-116        8/40  1   1                              2-Phenyl-3-(benzoyloxy)indone                                                                       168-169        4/20  1   1                              2-(4'-Chlorophenyl)-3-(pivaloyloxy)indone                                                           114-116        4/20  1   1                              3-(2-ethylbutanoyloxy)-2-(4'-isopropylphenyl)-                                                      γmax (μ): 5.63 (ester                                                               4/20  1   1                              indone                C═O); 5.8 (ketone C═O);                                               6.15 (enol C═C)                                     2-(4'-isopropylphenyl)-3-(pivaloyloxy)indone                                                        84-87          4/20  1   1                              2-(4'-isopropylphenyl)-3-(palmitoyloxy)indone                                                       γmax (μ): 5.59 (ester                                                               4/20  1   1                                                    C═O); 5.8 (ketone C═O);                                               6.13 (enol C═C)                                     __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________                                         Mite                                     Name                 M. P. ° C or IR                                                                  Herbicide                                                                           Adult                                                                             Ova                                  __________________________________________________________________________    2-(2'-Ethylphenyl)-3-pivaloyloxy-                                                                  γmax (μ): 5.51, 5.68                                                           4/20  1   1                                    indone               (ester C═O) 5.81                                                          (ketone C═O); 6.12                                                        enol C═C)                                            2-(2'-isopropylphenyl)-3-pivaloyloxy-                                                              γmax (μ): 5.5, 5.63                                                            4/20  1   1                                    indone               (ester C═O); 5.80                                                         (ketone C═O); 6.11                                                        (enol C═C)                                           2-(2',6'-diisopropyl)phenyl-3-pivaloyloxy-                                                         168-171   3/15  1   1                                    indone                                                                        3-(2-Ethylhexanoyloxy)-2-(2'-methoxyphenyl-                                                        γmax (μ): 5.5, 5.67                                                            4/20  1   1                                    indone               (ester C═O); 5.82                                                         (ketone C═O); 6.1                                                         (enol C═C)                                           2-(2'-Methoxyphenyl)-3-(neodecanoyloxy)-                                                           γmax (μ): 5.5, 5.62                                                            4/20  1   1                                    indone               (ester C═O) 5.79                                                          (ketone C═O); 6.1                                                         (enol C═C)                                           2-(2'-Methoxyphenyl)-3-(pivaloyloxy)-                                                              90-92     8/40  1   1                                    indone                                                                        2-(2'-Trifluoromethylphenyl)-3-                                                                    82-84     4/20  1   1                                    pivaloyloxy indone                                                            __________________________________________________________________________

It was also found that a limited class of the enol ester compoundsexhibit very powerful fumigant properties. The compounds having thisproperty are those in which the group attached to the carbonyl functionof the ester moiety is either alkyl or alkoxy having no more than fourcarbon atoms.

Two methods were used to evaluate fumigant properties:

Method 1

Fifty mg. of each compound were dissolved in 5 ml. of acetone and pouredinto a 20 cm. (bottom diameter) Pyrex No. 210 pie plate. The acetone wasallowed to evaporate leaving a deposit of approximately 160 μg. persquare cm. The plate was then placed in the bottom of a 50 pound metallard container (about 30 cm. in diameter and 34 cm. high). Two excisedbean plants, held in a 250 ml. Erlenmeyer flask containing 100 ml. oftap water and infested with eggs of the two-spotted mite, were placed inthe center of the pie plate. The container was held in the insectary(temperature 80°±5° F., 50±5% R. H.) for four days before mortalitydeterminations were made.

Method 2

Excised bean plants infested with egg forms of the two-spotted mite weredipped in an aqueous preparation (500 ppm) of the test compound. Thetreated plants were transferred to 250 ml. Erlenmeyer flasks containing100 ml. of tap water. Four flasks holding treated plants were evenlyspaced around a similar flask in which were placed untreatedmite-infested plants so that the leaves of the treated foliage were inclose proximity (1-3 inches) to the untreated plants. Four days latermortality determinations were made.

The results of these experiments are presented in Table VII below.Mortality ratings were as follows:

5 = 80-100% control

3 = moderate control as compared to an unexposed standard

1 = no significant control

                                      TABLE VII                                   __________________________________________________________________________    FUMIGANT TOXICITY                                                                                               Fumigant Toxicity                           Compound                          Method 1                                                                           Method 2                               __________________________________________________________________________    2-(2',4',6'-Trimethylphenyl)-3-(acetoxy)indone                                                                  5    5                                      2-(2',4',6'-Trimethylphenyl)-3-(propionyloxy)indone                                                             5    5                                      2-(2',4'6'-Trimethylphenyl)-3-(isobutyryloxy)indone                                                             5    5                                      2-(2',4',6'-Trimethylphenyl)-3-(pivaloyloxy)indone                                                              5    5                                      2-(2',4',6'-Trimethylphenyl)-3-(2-ethylhexanoyloxy)indone                                                       1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(cyclohexanoyloxy)indone                                                         1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(neodecanoyloxy)indone                                                           1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(isopropoxycarbonyloxy)indone                                                    5    3                                      2-(2',4',6'-Trimethylphenyl)-3-(octadecanoyloxy)indone                                                          1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(3-methoxycarbonylpropionyloxy)indone                                            1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(4-chlorobutyryloxy)indone                                                       1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(methoxyacetoxy)indone                                                           1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(endo-exo norborn-5-en-2-carbonyloxy)-                                           1    1                                      indone                                                                        2-(2',4',6'-Trimethylphenyl)-3-(undec-9-enoyloxy)indone                                                         1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(dodecyloxycarbonyloxy)indone                                                    1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(2-ethylhexyloxycarbonyloxy)indone                                               1    1                                      2-(2',4',6'-Trimethylphenyl)-3-(octylthiocarbonyloxy)indone                                                     1    1                                      2(2',4',6'-Trimethylphenyl)-3-(cyclopent-2-en-1-ylacetoxy)indone                                                1    1                                      2-(2' ,6'-Dichlorophenyl)-3-(pivaloyloxy)indone                                                                 --   3                                      __________________________________________________________________________

The fumigant properties exhibited by certain of the enol esters isconsidered highly important due to the fact that these compounds show ahigh level of activity, even when coverage on an infested plant isdiscontinuous. These fumigant properties may greatly enhance theuniformity and extent to which control may be achieved in fieldapplications under adverse circumstances.

Side by side comparison tests were conducted to determine theeffectiveness of selected enol ester compounds relative to(bis(p-chlorophenyl)trichlorethanol) a miticide sold under the trademarkKelthane and ovex (p-chlorophenyl-p-chlorobenzene sulfonate) two widelyused commercial miticides. The tests were conducted in accordance withthe procedures described above at various dilutions of the testcompounds in order to determine the LD₅₀ and LD₉₅ values (concentrationof test compound required to kill 50 and 95 percent respectively of themite population.

                  TABLE VIII                                                      ______________________________________                                                    Mite Adults (ppm)                                                                         Mita Ova (ppm)                                        Compound      LD.sub.50                                                                              LD.sub.95                                                                              LD.sub.50                                                                            LD.sub.95                              ______________________________________                                        2-(2',4',6'-trimethyl-                                                                       5       170      3      9                                      phenyl)-3-pivaloyloxy                                                         indone                                                                        2-(2',4',6'-trimethyl-                                                                      25       230      2      6                                      phenyl)-3-(2-ethyl-                                                           hexanoyloxy)indone                                                            Kelthane      20        65      370    700                                    Ovex          1000     --       200    300                                    ______________________________________                                    

Both of the enol ester compounds tested are dramatically superior toKelthane and ovex for control of mite ova and also show good control ofmite adults.

Experiments were also conducted to determine the phytotoxicity ofrepresentative enol ester compositions with respect to healthy freshplants. Solutions of the desired compound were prepared as describedabove to provide a concentration of 2500 parts per million of the enolester compound. The test plants were sprayed in accordance with theprocedure described above for the Mite Foliage Spray Test so as todeliver approximately 100 milliliters of test solution to the leaves ofeach plant tested. The sprayed plants and controls were set aside forapproximately 1 hour to allow the solutions to dry and were then placedin the greenhouse. After ten days the plants were visually inspected todetermine the extent of foliage injury. A rating of 1 indicates noperceptible injury; 5 indicates the plant was dead and ratings of 2, 3and 4 indicate intermediate degrees of injury based upon the number andextent to which leaves were injured.

                                      TABLE IX                                    __________________________________________________________________________                                     Phytotoxicity Rating                         Compound                         Bean                                                                             Corn                                                                             Tomato                                                                             Cotton                            __________________________________________________________________________    3-(2-Ethylhexanoyloxy)-2-(2'-fluorophenyl)indone                                                               2  2  1    1                                 2-(2'-Chlorophenyl)-3-(pivaloyloxy)indone                                                                      1  1  1    1                                 2-(2'-Chlorophenyl)-3-(2-methylpentanoyloxy)indone                                                             1  1  1    1                                 2-(2'-Bromophenyl)-3-(pivaloyloxy)indone                                                                       1  1  1    1                                 2-(2'-Chlorophenyl)-3-(stearoyloxy)indone                                                                      1  1  1    1                                 2-(2'-Chloro-6'-methylphenyl)-3-(pivaloyloxy)indone                                                            1  1  3    2                                 2-(2'-Methylphenyl)-3-(pivaloyloxy)indone                                                                      1  1  1    1                                 3-(2-Ethylhexanoyloxy)-2-(2'-methylphenyl)indone                                                               1  1  1    1                                 2-(2'Methylphenyl)-3-(palmitoyloxy)indone                                                                      1  1  1    1                                 2-(2'-Methylphenyl)-3-(neodecanoyloxy)indone                                                                   1  1  1    1                                 2-(2',4'-Dimethylphenyl)-3-(stearoyloxy)indone                                                                 1  1  1    1                                 2(2',4'-Dimethylphenyl)-3-(lauroyloxy)indone                                                                   1  1  1    1                                 2(2',4'-Dimethylphenyl)-3-(2-methylpentanoyloxy)indone                                                         1  1  1    1                                 2-(2',6'-Dimethylphenyl)-3-(pivaloyloxy)indone                                                                 1  1  3    2                                 2-(2',5'-Dimethylphenyl)-3-(neodecanoyloxy)indone                                                              1  1  1    1                                 (mixture of isomers)                                                          2-(2',5'-Dimethylphenyl)-3-(2-ethylbutanoyloxy)indone                                                          1  1  1    1                                 2-(2',5'-Dimethylphenyl)-3-(tridecanoyloxy)indone                                                              2  2  1    1                                 2-(2',6'-Dimethyl-4-t-butylphenyl)-3-(pivaloyloxy)indone                                                       1  1  1    1                                 2-(2',6'-Dimethyl-4-methoxyphenyl)-3-(pivaloyloxy)indone                                                       1  1  1    1                                 3-(Pivaloyloxy)-2-(6'-methoxy-2',3',4'-trimethylphenyl)indone                                                  1  1  1    1                                 3-(2-Ethylhexanoyloxy)-2-(1-naphthyl)indone                                                                    1  1  1    1                                 2-(2',4',6'-Trimethylphenyl)-3-(acetoxy)indone                                                                 1  1  2    2                                 2-(2',4',6'-Trimethylphenyl)-3-(propionyloxy)indone                                                            1  2  2    1                                 2-(2',4',6'-Trimethylphenyl)-3-(isobutyryloxy)indone                                                           1  4  2    2                                 2-(2',4',6'-Trimethylphenyl)-3-(pivaloyloxy)indone                                                             1  3  3    3                                 2-(2',4',6'-Trimethylphenyl)-3-(2-ethylhexanoyloxy)indone                                                      2  1  1    1                                 2-(2',4',6'-Trimethylphenyl)-3-(cyclohexanoyloxy)indone                                                        1  1  2    2                                 2-(2',4',6'-Trimethylphenyl)-3-(neodecanoyloxy)indone                                                          2  2  1    1                                 (mixture of isomers)                                                          2-(2',4',6'-Trimethylphenyl)-3-(isopropoxycarbonyloxy)indone                                                   2  1  1    1                                 2-(2',4',6'-Trimethylphenyl)-3-(octadecanoyloxy)indone                                                         1  1  1    1                                 2-(2',4',6'-Trimethylphenyl)-3-(3-methoxycarbonyl propionyloxy)-                                               1  1  1    1                                 indone                                                                        2-(2',4',6'-Trimethylphenyl)-3-(endo-exo norborn-5-en-2-                                                       1  1  1    2                                 carbonyloxy)indone                                                            2-(2',4',6'-Trimethylphenyl)-3-(undec-9-enoyloxy)indone                                                        2  2  2    1                                 2-(2',4',6'-Trimethylphenyl)-3-(dodecyloxycarbonyloxy)indone                                                   1  2  1    1                                 2-(2',4',6'-Trimethylphenyl)-3-(2-ethylhexyloxycarbonyloxy)-                                                   1  2  1    1                                 indone                                                                        2-(2',4',6'-Trimethylphenyl)-3-(octylthiocarbonyloxy)indone                                                    1  1  1    1                                 2-(2',4',6'-Trimethylphenyl)-3-(cyclopert-2-en-1-ylacetoxy)indone                                              1  1  1    2                                 2-(2',4',6'-Trimethylphenyl)-3-(4-chlorobutyryloxy)indone                                                      1  2  2    2                                 2-(2',4',6'-Trimethylphenyl)-3-(methoxyacetoxy)indone                                                          1  1  1    1                                 __________________________________________________________________________

The test results presented in Table IX above, indicate that thesematerials may be used on certain economic crops without danger ofphytotoxicity even at application rates considerably higher than wouldnormally be used in field applications.

In Table X below test results obtained in small scale field testing arepresented to demonstrate the significantly higher degree of mite controlachieved with the enol esters as opposed to the parent indandionecompound from which the enol ester is prepared.

Selected enol ester compositions were evaluated in small scale fieldtests to determine whether the excellent miticidal properties observedin greenhouse testing would be obtained under actual conditions of fielduse. Comparison tests were made with the parent indandione compositionsof the enol esters selected for field evaluation to establish whetherthe superior results observed in laboratory evaluations would carry overinto actual conditions of use in the field. Although normally, fieldtests conditions are difficult to control precisely, the resultsobtained from these tests demonstrate conclusively that the enol estersof this invention are consistently and significantly superior to theparent indandione compounds in miticidal activity under actualconditions of use in the field and that the outstanding miticidalproperties observed in laboratory testing are maintained under fieldconditions.

In Test I 500 ppm aqueous dispersions were prepared as described above.In tests II and III various dilutions of the test compounds ranging from125 ppm to 1000 ppm were prepared and used. In each case the testdispersions were applied to a minimum of two replicate test plotsmeasuring five feet in length and containing healthy young Tendergreenbean plants which had previously been infested with two spotted mite(Tetranychus urticae (Koch)). Dispersions of the test compounds at eachconcentration level were applied to individual replicate plots usingone-half gallon garden sprayers equipped with spray nozzles to applyapproximately 250 ml of test solution to each replicate. Theeffectiveness of the treatment was determined at intervals followingapplication, by microscopic examination of five leaves selected atrandom from each replicate plot. The degree of effectiveness for eachleaf was rated on a scale of from 1 to 5 with 1 indicating no control inreference to a standard sprayed with a mixture of solution less testcompound and 5 indicating complete control. The results obtained frominspection of sample leaves were then averaged to give a numericalindication of the degree of control for each compound tested at theconcentration applied.

The following compounds were evaluated in these experiments:

Compound A: 2-(2',4',6'-trimethylphenyl)-1,3-indandione

Compound A1: 2-(2',4',6'-trimethylphenyl)-3-(pivaloyloxy)indone

Compound A2: 3-(3-chlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone

Compound A3: 3-(2-chlorobenzoyloxy)-2-(2',4',6'-trimethylphenyl)indone

Compound B: 2-(2',6'-dichlorophenyl)-1,3-indandione

Compound B1: 2-(2',6'-dichlorophenyl)-3-(pivaloyloxy)indone

Compound B2: 3-(3-chlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone

Compound B3: 3-(2-chlorobenzoyloxy)-2-(2',6'-dichlorophenyl)indone

The results of these tests are recorded in Table X below:

                                      TABLE X                                     __________________________________________________________________________    AVERAGE MITE CONTROL RATINGS SMALL SCALE FIELD TESTS                          Conc. 1st. Reading*   2nd Reading                                                                              3rd Reading                                  (ppm)                                                                             A A1                                                                              A2                                                                              A3                                                                              B B1                                                                              B2                                                                              B3                                                                              A A1                                                                              A2                                                                              A3                                                                              B B1                                                                              B2                                                                              B3                                                                              A A1                                      __________________________________________________________________________    TEST I                                                                        500 1.0                                                                             4.0                                                                             1.5                                                                             2.5                                                                             1.5                                                                             3.5                                                                             3.0                                                                             3.0                                                                             1.0                                                                             3.5                                                                             2.0                                                                             2.0                                                                             2.0                                                                             4.0                                                                             3.0                                                                             2.5                                                                             --                                                                              --                                      TEST II                                                                       250 1.0                                                                             3.0                                                                             --                                                                              --                                                                              3.7                                                                             2.3                                                                             --                                                                              --                                                                              1.3                                                                             4.0                                                                             --                                                                              --                                                                              2.3                                                                             3.7                                                                             --                                                                              --                                                                              --                                                                              --                                      500 2.7                                                                             2.3                                                                             --                                                                              --                                                                              3.0                                                                             3.0                                                                             --                                                                              --                                                                              1.7                                                                             4.7                                                                             --                                                                              --                                                                              3.3                                                                             3.3                                                                             --                                                                              --                                                                              --                                                                              --                                      1000                                                                              --                                                                              --                                                                              --                                                                              --                                                                              2.0                                                                             3.3                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              3.3                                                                             4.7                                                                             --                                                                              --                                                                              --                                                                              --                                      TEST III                                                                      125 --                                                                              1.7                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              2.3                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              1.7                                     250 1.0                                                                             3.0                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              2.0                                                                             4.0                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              3.7                                     500 1.3                                                                             3.0                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              1.7                                                                             4.0                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4.5                                     1000                                                                              3.3                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              3.3                                                                             --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              2.3                                                                             --                                      __________________________________________________________________________     *1st Reading: Test I, 4 days after application, Tests II & III 3 days         after application                                                             2nd Reading: Test I, 8 days after application, Tests II & III 7 days afte     application                                                                   3rd Reading: 21 days after application.                                       Dashes indicate no test conducted.                                       

The test results from the small scale field tests demonstrate the veryhigh degree of miticidal activity possessed by the enol ester compounds(Compounds A1-A3 and B1-B3). The improvement in the degree of controlfrequently observed for the enol ester compounds in the second and thirdreadings is indicative of the high residual activity and excellentovicidal activity possessed by these compounds particularly whencompared to the parent indandione compounds (Compounds A and B).

The new compounds of this invention may be applied as miticides andherbicides according to methods known to those skilled in the art.Pesticidal compositions containing the compounds as the active toxicantwill usually comprise a carrier and/or a diluent, either liquid orsolid.

Suitable liquid diluents or carriers include water, petroleumdistillates, or other liquid carriers with or without surface activeagents. Liquid concentrates may be prepared by dissolving one of thesecompounds with a non-phytotoxic solvent such as acetone, xylene, ornitrobenzene and dispersing the toxicants in water with the aid ofsuitable surface active smulsifying and dispersing agents.

The choice of dispersing and emulsifying agents and the amount employedis dictated by the nature of the composition and the ability of theagent to facilitate the dispersion of the toxicant. Generally, it isdesirable to use as little of the agent as is possible, consistent withthe desired dispersion of the toxicant in the spray so that rain doesnot re-emulsify the toxicant after it is applied to the plant and washit off the plant. Nonionic, anionic, or cationic dispersing andemulsifying agents may be employed, such as the condensation products ofalkylene oxides with phenol and organic acids, alkyl, aryl sulfonates,complex ether alcohols, quaternary ammonium compounds, and the like.

In the preparation of wettable powder or dust or granulatedcompositions, the active ingredient is dispersed in and on anappropriately divided solid carrier such as clay, talc, bentonite,diatomaceous earth, fullers earth, and the like. In the formulation ofthe wettable powders the aforementioned dispersing agents as well aslignosulfonates can be included.

The required amount of the toxicants contemplated herein may be appliedper acre treated in from 1 to 200 gallons or more of liquid carrierand/or diluent or in from about 5 to 500 pounds of inert solid carrierand/or diluent. The concentration in the liquid concentrate will usuallyvary from about 10 to 95 percent by weight and in the solid formulationsfrom about 0.5 to about 90 percent by weight Satisfactory sprays, dusts,or granules for general use contain from about 1/4 to 15 pounds ofactive toxicant per acre.

The pesticides contemplated herein prevent attack by mites upon plantsor other material to which the pesticides are applied, and they havehigh residual toxicity. The toxicants are chemically inert and they arecompatible with substantially any other constituents of the sprayschedule. When used as miticides they will normally be applied to thefoliage of the plants to be treated. When used as herbicides they may beused in the soil or directly upon the seeds to be treated.

What is claimed is:
 1. A pre-emergent herbicide comprising an extenderand as an active toxicant a herbicidally effective amount of a compoundhaving the structural formula: ##STR6## wherein: R¹ is hydrogen, halogenor an organic radical;R² is hydrogen, methyl, ethyl, methoxy, ethoxy,fluorine, chlorine, bromine, trichloromethyl, trifluoromethyl or mixedchlorofluoromethyl; R³ is hydrogen, lower alkyl, lower alkoxy, fluorine,chlorine, bromine, nitro, acylamido, trichloromethyl, trifluoromethyl ormixed chlorofluoromethyl; R⁴ is methyl, ethyl, methoxy, ethoxy,fluorine, chlorine or bromine; R⁵ is hydrogen, lower alkyl, lowerhaloalkyl, lower alkoxy, acylamido, fluorine, chlorine or bromine; R⁶ ishydrogen, lower alkyl, lower alkoxy, fluorine, chlorine, bromine,trifluoromethyl, trichloromethyl or acylamido; n is a small whole numberfrom 1 to 4; and R² and R⁵ or R⁴ and R⁵ taken together, may be--CH═CH--CH═CH-- with the proviso that when R⁴ is ethyl, methoxy orethoxy R², R³ and R⁵ may not all be hydrogen.
 2. A pre-emergentherbicide in accordance with claim 1 wherein R¹ is hydrogen chloro,bromo, fluoro or an unsubstituted or substituted organic radicalselected from the group consisting of: alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl, alkylthioalkyl, alkoxyalkyl,alkoxycarbonylalkyl, arylalkyl, aryloxyalkyl, arylthioalkyl, aryl,alkylaryl, alkoxyaryl, alkoxy, alkylthio, aryloxy, arylthio,heterocyclic acylamido alkyl carbamoylalkyl and amino radicals havingthe formula: ##STR7## wherein R⁷ is hydrogen, alkyl, alkenyl, alkynyl,cycloalkyl or aryl and R⁸ is alkyl, alkenyl, alkynyl, cycloalkyl or arylor R⁷ and R⁸, taken together, form a lower alkylene or lower dialkyleneether linkage.
 3. A pre-emergent herbicide, adult miticide and miteovicide comprising an extender and as an active toxicant anherbicidally, miticidally or mite ovicidally effective amount of acompound having the structural formula: ##STR8## wherein: R¹ ischlorine, bromine, fluorine or an organic radical, which does notinterfere with hydrolysis of the ester moiety to which it is attached;R²is hydrogen, methyl, ethyl, methoxy, fluorine, chlorine or bromine; R³is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorine or bromine;R⁴ is methyl, ethyl, methoxy, fluorine, chlorine or bromine; R⁵ ishydrogen, lower alkyl, lower alkoxy, fluorine, chlorine or bromine; R⁶is hydrogen, lower alkyl, lower alkoxy, fluorine chlorine or bromine;and n is a small whole number from 1 to 4 with the proviso that when R⁴is ethyl or methoxy, R², R³ and R⁵ may not all be hydrogen.
 4. Aherbicide, miticide and ovicide in accordance with claim 3 wherein R¹ isfluorine, chlorine, bromine or an unsubstituted or substituted organicradical selected from the group consisting of: alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl, alkylthioalkyl, alkoxyalkyl,alkoxycarbonylalkyl, arylalkyl, aryloxyalkyl, arylthioalkyl, aryl,alkylaryl, alkoxyalkyl, alkoxy, alkylthio, aryloxy, arylthio, aryloxy,arylthio, heterocyclic, acylamidoalkyl carbamoylalkyl and amino radicalshaving the formula: ##STR9## wherein R⁷ is hydrogen, alkyl, alkenyl,alkynyl, cycloalkyl or aryl and R⁸ is alkyl, alkenyl, alkynyl,cycloalkyl or aryl or R⁷ and R⁸, taken together, form a lower dialkyleneether linkage.
 5. A herbicide, miticide and ovicide in accordance withclaim 3 wherein R¹ is aryl having at least one unsubstituted carbon inthe ortho position.
 6. A herbicide, miticide and ovicide in accordancewith claim 3 wherein R² is hydrogen, methyl, chlorine or bromine and R⁴is methyl, chlorine or bromine.
 7. A pre-emergent herbicide, adultmiticide and mite ovicide comprising an extender and as an activetoxicant an herbicidally, miticidally or mite ovicidally effectiveamount of a compound having the structural formula: ##STR10## wherein R¹is chlorine, bromine, fluorine or an organic radical which does notinterfere with hydrolysis of the ester moiety to which it is attached.8. A herbicide, miticide and ovicide in accordance with claim 7 whereinR¹ is phenyl.
 9. A herbicide, miticide and ovicide in accordance withclaim 7 wherein R¹ is heptadecyl.
 10. A herbicide, miticide and ovicidein accordance with claim 7 wherein R¹ is isopropoxy.
 11. A herbicide,miticide and ovicide in accordance with claim 7 wherein R¹ isoctadecyloxy.
 12. A pre-emergent herbicide, adult miticide and miteovicide comprising an extender and as an active toxicant anherbicidally, miticidally or mite ovicidally effective amount of acompound having the structural formula: ##STR11## wherein R¹ ischlorine, bromine, fluorine or an organic radical which does notinterfere with the hydrolysis of the ester moiety to which it isattached.
 13. A pre-emergent herbicide, adult miticide and mite ovicidecomprising an extender and as an active toxicant an herbicidally,miticidally, or mite ovicidally effective amount of a compound havingthe structural formula: ##STR12## wherein: R¹ is alkyl;R² is hydrogen,methyl, ethyl, methoxy, fluorine, chlorine or bromine; R³ is hydrogen,lower alkyl, lower alkoxy, fluorine, chlorine or bromine; R⁴ is methyl,ethyl, methoxy, fluorine, chlorine or bromine; R⁵ is hydrogen, loweralkyl, lower alkoxy, fluorine, chlorine or bromine; R⁶ is hydrogen,lower alkyl, lower alkoxy, fluorine, chlorine or bromine; and n is asmall whole number from 1 to 4 with the proviso that when R⁴ is ethyl ormethoxy, R², R³ and R⁵ may not all be hydrogen.
 14. A herbicide,miticide and ovicide in accordance with claim 13 wherein R¹ is alkylhaving from 1 to 4 carbon atoms.
 15. A pre-emergent herbicide, adultmiticide and mite ovicide comprising an extender and as an activetoxicant an herbicidally, miticidally, or mite ovicidally effectiveamount of a compound having the structural formula: ##STR13## wherein R¹is alkyl;
 16. A herbicide, miticide and ovicide in accordance with claim15 wherein R¹ is alkyl having from 1 to 4 carbon atoms.
 17. A herbicide,miticide and ovicide in accordance with claim 15 wherein R¹ is methyl.18. A herbicide, miticide and ovicide in accordance with claim 15wherein R¹ is ethyl.
 19. A herbicide, miticide and ovicide in accordancewith claim 15 wherein R¹ is isopropyl.
 20. A herbicide, miticide andovicide in accordance with claim 15 wherein R¹ is t-butyl.
 21. Aherbicide, miticide and ovicide in accordance with claim 15 wherein R¹is 1-ethylpentyl.
 22. A pre-emergent herbicide, adult miticide and miteovicide comprising an extender and as an active toxicant asherbicidally, miticidally, or mite ovicidally effective amount of acompound having the structural formula: ##STR14## wherein R¹ is alkyl.23. A method of controlling plant pests which comprises applying to theseeds of such plant pests a herbicidally effective amount of a compounddescribed in claim
 1. 24. A method of controlling mites which comprisessubjecting them to a miticidal amount of a compound described in claim3.
 25. A method of controlling mites which comprises subjecting them toa miticidal amount of a compound described in claim
 4. 26. A method ofcontrolling mites which comprises subjecting them to a miticidal amountof a compound described in claim
 6. 27. A method of controlling miteswhich comprises subjecting them to a miticidal amount of a compounddescribed in claim
 7. 28. A method of controlling mites which comprisessubjecting them to a miticidal amount of a compound described in claim12.
 29. A method of controlling mites which comprises subjecting them toa miticidal amount of a compound of the formula: ##STR15## wherein: R¹is alkyl;R² is hydrogen, methyl, ethyl, methoxy, fluorine, chlorine orbromine; R³ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorineor bromine; R⁴ is methyl, ethyl, methoxy, fluorine, chlorine or bromine;R⁵ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorine orbromine; R⁶ is hydrogen, lower alkyl, lower alkoxy, fluorine, chlorineor bromine; and n is a small whole number from 1 to 4 with the provisothat when R⁴ is ethyl or methoxy, R², R³ and R⁵ may not all be hydrogen.30. A method according to claim 29 wherein R¹ is lower alkyl having from1 to 4 carbon atoms.
 31. A method according to claim 29 wherein R², R³and R⁴ are methyl and R⁵ and R⁶ are hydrogen.
 32. A method according toclaim 29 wherein R² and R⁴ are chlorine and R³, R⁵ and R⁶ are hydrogen.33. A method according to claim 29 wherein R¹ is lower alkyl having from1 to 4 carbon atoms; R² and R⁴ are chlorine and R³, R⁵ and R⁶ arehydrogen.
 34. A herbicide, miticide and ovicide in accordance with claim22 wherein R¹ is alkyl having from 1 to 4 carbon atoms.